Sodium Iodide → 1-Iodo-4-phenoxybut-2-yne

HRID 1607819Notes

Reaction equation

HRID 1607819 reaction equation
CS(Cl)(=O)=O.[O:6]([CH2:13][C:14]#[C:15][CH2:16]O)[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1.C(=O)(O)[O-].[Na+].S([O-])(=O)(=O)C.[I-:28].[Na+]>C(Cl)Cl.CC(C)=O.C(N(CC)CC)C>[I:28][CH2:16][C:15]#[C:14][CH2:13][O:6][C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][CH:8]=1

Participants

9

Reactant 5

HCID 5238Sodium IodideHCID 31297Methanesulfonyl chlorideHCID 85257MethanesulfonateHCID 516892Sodium Bicarbonate2×HCID 160466794-Phenoxybut-2-yn-1-ol

Product 1

HCID 198494611-Iodo-4-phenoxybut-2-yneYield 68.6%

Reagents, catalysts & solvents 3

HCID 180AcetoneSolvent2×HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Conditions

Temperature
0 °C

Procedure

1.432 ml (2.12 g, 0.0185 mol) of methanesulfonyl chloride was added dropwise to a solution of 2 g of 4-phenoxybut-2-yn-1-ol and 2.77 ml of triethylamine in 30 ml of methylene chloride at such a rate to maintain the reaction temperature at 0° C. After addition, the resulting mixture was stirred for 30 minutes at 0° C. Then the reaction mixture was poured into 30 ml of saturated aqueous sodium bicarbonate solution and extracted with methylene chloride. The organic extracts were dried over sodium sulfate and the solvent removed by evaporation in vacuo and thus crude 4-phenoxy-but-2-yn-1-ol methanesulfonate was obtained. The foregoing crude mesylate was dissolved in 15 ml of acetone and treated with a solution of 5.55 g of sodium iodide and 1.049 g of sodium bicarbonate in 30 ml of acetone. The reaction mixture was stirred for 1 hour at room temperature and then the solvent was removed under reduced pressure. The residue was diluted with water (25 ml) and extracted with methylene chloride, (3×30 ml) the organic extracts were dried and the solvent removed by evaporation. The residue was purified by silica gelcolumn chromatography (50 g) using hexane:ethyl acetate (95:5) as eluant, to yield 2.3 g (62%) of 1-iodo-4-phenoxybut-2-yne. The product was stored in the refrigerator.

Workup

  1. additionAfter addition
  2. extractionextracted with methylene chloride
  3. dry with materialThe organic extracts were dried over sodium sulfate
  4. customthe solvent removed by evaporation in vacuo
  5. customthus crude 4-phenoxy-but-2-yn-1-ol methanesulfonate was obtained
  6. stirringThe reaction mixture was stirred for 1 hour at room temperature
  7. customthe solvent was removed under reduced pressure
  8. additionThe residue was diluted with water (25 ml)
  9. extractionextracted with methylene chloride, (3×30 ml) the organic extracts
  10. customwere dried
  11. customthe solvent removed by evaporation
  12. customThe residue was purified by silica gelcolumn chromatography (50 g)

Sources & evidence

ORD record
ord-08e8a21a3e804c52952a14c569e69193
Source dataset
uspto-grants-1989_09
Patent number
US04867915

Reaction notes

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